Method of coating a substrate for adhesive bonding

ABSTRACT

According to at least one aspect of the present invention, a coated substrate surface is provided. In at least one embodiment, the coated substrate surface includes a substrate surface, and a high-velocity impact polymer reaction coating for promoting adhesive bonding, the coating having first and second opposing surfaces, the first opposing surface being adjacent to the substrate surface. In at least another embodiment, the high-velocity impact polymer reaction coating is formed by depositing a polymer reaction compound onto the substrate surface with a high-velocity impact device at a velocity in the range of 10 to 200 meters per second, the polymer reaction compound being formed from substantially random fragmentation of prepolymer molecules.

CROSS-REFERENCE TO RELATED APPLICATION

This application is a divisional of U.S. application Ser. No. 11/162,746filed Sep. 21, 2005.

BACKGROUND

1. Field of the Invention

One aspect of the present invention relates to a method of coating asubstrate for adhesive bonding.

2. Background Art

In producing many articles, often it is necessary to join dissimilarmaterials. In many cases, one or both of the materials must have theirsurface properties adjusted. Adjusting surface properties of materialsin manufacturing often involve surface treatment technologies.Non-limiting examples of these surface properties include the surfaceenergy, chemical inertness, conductivity, receiving dyes, and adhesion.Non-limiting examples of applications using surface treatment andpreparation include anti-corrosion coatings on corrodible metals such asiron and steel; bio-compatible coatings on implants; waterproof layerson electronics; and adhesives on glass.

Applying coatings, adhesives, sealants, and elastomers (CASE) tosubstrates often require particular care in treating or pre-treating thesurface to avoid adhesive failure between the substrate and the appliedCASE compounds. Many CASE application processes involve steps of (a)cleaning or roughening the surface, (b) applying a primer that eitherbonds to the surface or etches it, and (c) applying an enhancement agentthat adds additional bonding functionality. CASE compounds are used inindustries including construction, automotive, medical, dental,labeling, electronics, and packaging.

In the automotive industry, CASE compounds are used in conjunction withglass glazing processes. Disadvantageously, automotive glazing glass issusceptible to breakage from mechanical shocks striking at its edges. Asa consequence, the edges are typically encapsulated. In oneencapsulation method, a frame connects the automotive glazing glass tothe vehicular superstructure. The frame thereby borders portions of theglass. In one method for bonding the glass and frame components, theglazing glass is cleaned with a solvent, a primer containing a couplingagent to chemically modify the surface is applied to the surface, andfinally, a thicker layer of a paint-like compound which bonds well tothe frame is applied. In this example, properly aligning the two layers,i.e. primer and paint-like compound layers' present difficulties becausethe primer becomes effectively transparent on glass when dried and thesecond coating is opaque, prohibiting accurate alignment when theapplication width is wider than that of the primer coat.

When glazing glass is used as a windshield, it is intended to preventmass and energy transfer into the passenger compartment, such as wind,rain, debris, and infrared heat, while contributing to passenger safetyby increasing structural integrity during vehicle crash and rolloverscenarios. In some instances, the glazing glass is not a homogeneoussurface as it may have frits in some area to shade from infrared,ultraviolet and other wavelengths of light. Likewise, it may have areasthat are tinted. Further, it may have gaps in these features to permitapplication of fasteners. These gaps may need labor-intensive maskingduring application of a second layer of sealant.

Other aspects of joining dissimilar materials include desires to improveaccuracy of manufacturing, productivity, levels of automation,reliability, and/or manufacturability while decreasing harmful sideeffects, quantity of materials used, and/or waste of energy andmaterials. For example, some CASE compounds have substantial amounts ofwaste. Often coupling agent primers are less than 1% active agent and99% carrier solvent. In another example, cleaning materials have harmfulside affects such as flammability and/or noxious solvents like isopropylalcohol or toluene. In other cases, paint-like layers often have to airdry within 30 seconds and so use volatile solvents. Energy and money arewasted to remediate these emissions and to protect workers' health.

Recently, plasma polymerization has been developed as a tool to modifymaterial surfaces while improving manufacturability, levels ofautomation, and accuracy of manufacturing, while decreasing harmful sideeffects as well as waste of energy and materials.

There are different types of plasmas that are defined by their outputtemperature, their pressure conditions, as well as the equilibrationstate regarding the chemistry and thermal state. For example, there areplasmas created under subambient pressure conditions. Examples include ahigh plasma density mode and a low plasma density mode plasma generatedwith a magnetron which is typically used in physical vapor deposition.Other ambient pressure examples include glow discharge,inductively-coupled, and recombining plasmas. The glow discharge ischaracterized by low velocity movement of gas of a few meters/second. Itfeatures both thermal and chemical non-equilibrium. Aninductively-coupled plasma has low to moderate gas movement. It featureslocal thermal equilibria. The recombining nitrogen or air plasmas havehigh gas velocities of approximately 1 km/sec and feature chemicalequilibria. Additional examples of classes of plasmas are determined bytheir ionization methods such as microwave resonance and electricaldischarge.

When plasmas are applied to high volume production processes outside alaboratory, additional manufacturability and automation considerationsarise such as speed of operation, compatibility with substrates, andcontamination.

In many applications, the plasma treatments occur quickly, typically onthe order of nanoseconds to a few minutes, which effectively precludebatch vacuum techniques such as physical vapor deposition.

The high temperature plasmas may thermally combust or thermally shocksubstrates, especially ones with low thermal conductivity as well as lowmelting or combustion points.

In addition, some surfaces are imperfect, such as those having dust,organic body oils, and debris from shipment and handling.

In light of the foregoing, what is needed is a method that improvesaccuracy of manufacturing, productivity, levels of automation,reliability, and/or manufacturability while decreasing harmful sideeffects, quantity of materials used, and/or waste of energy andmaterials for a high volume production process for preparing a surfacefor joining two dissimilar materials or to receive CASE compounds.

SUMMARY

An embodiment of the present invention is a method for depositing acoating where the surface is cleaned during a first time period, anddepositing a high-velocity impact polymer reaction coating on thesurface at ambient air pressure during a second time period using anatmospheric pressure air plasma (APAP).

Another embodiment of the present invention is a method for applying acoating involving mixing a prepolymer vapor with a carrier gas or as amist of small droplets, introducing that mixture into an atmosphericpressure air plasma to form a polymer reaction compound, and thenapplying the polymer reaction compound with high-velocity impact drivenby the exiting gases of the atmospheric pressure air plasma.

A further embodiment of the present invention is a coated glass surface,having a glass surface such as a new or older windshield to which ahigh-velocity impact polymer reaction coating is directly applied usingan atmospheric pressure air plasma after cleaning. An additional aspectof this embodiment includes having a second layer such as a sealant tojoin dissimilar materials, for example a windshield and frame. Anotheraspect of this embodiment includes making composite depositions of thehigh-velocity impact polymer reaction coating on a surface using eithermultiple travel paths or multiple APAPs traveling in a substantiallysequential or substantially parallel travel path.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows an example of the application of certain embodiments of thepresent invention on a vehicle;

FIG. 2 shows an example of deposition of high-velocity impact polymerreaction coating onto a surface of certain embodiments of the presentinvention;

FIG. 3 shows another example of deposition of high-velocity impactpolymer reaction coating onto a surface of certain embodiments of thepresent invention;

FIG. 4 shows an example of a coated glass surface having a high-velocityimpact polymer reaction coating, a second layer, and a frame of certainembodiments of the present invention;

FIG. 5 shows an example of a coated glass surface having a compositehigh-velocity impact polymer reaction coating of certain embodiments ofthe present invention;

FIG. 6 shows an example of a coated glass surface having a compositehigh-velocity impact polymer reaction coating of certain embodiments ofthe present invention;

FIG. 7 shows an example of a prepolymer delivery system according tocertain embodiments of the present invention; and

FIG. 8 shows a cross section of an atomizing collar taken about the line8-8.

DETAILED DESCRIPTION OF EMBODIMENTS OF THE PRESENT INVENTION

Reference will now be made in detail to compositions, embodiments, andmethods of the present invention known to the inventors. However, itshould be understood that disclosed embodiments are merely exemplary ofthe present invention which may be embodied in various and alternativeforms. Therefore, specific details disclosed herein are not to beinterpreted as limiting, rather merely as representative bases forteaching one skilled in the art to variously employ the presentinvention.

Except where expressly indicated, all numerical quantities in thisdescription indicating amounts of material or conditions of reactionand/or use are to be understood as modified by the word “about” indescribing the broadest scope of the present invention. Practice withinthe numerical limits stated is generally preferred.

The description of a group or class of materials as suitable for a givenpurpose in connection with the present invention implies that mixturesof any two or more of the members of the group or class are suitable.Description of constituents in chemical terms refers to the constituentsat the time of addition to any combination specified in the description,and does not necessarily preclude chemical interactions amongconstituents of the mixture once mixed. The first definition of anacronym or other abbreviation applies to all subsequent uses herein ofthe same abbreviation and applies mutatis mutandis to normal grammaticalvariations of the initially defined abbreviation. Unless expresslystated to the contrary, measurement of a property is determined by thesame technique as previously or later referenced for the same property.

FIG. 1 shows on an automobile 1 having areas where dissimilar materialsare joined, including the windshield 8, side windows 9, sunroofs 13,rear windows, and mirrors 11. Other areas where coatings, adhesives,sealants, and elastomers are used include, but are not limited to, metalsurfaces, such as hubcaps 18; elastomeric trim strips for decoration 14;interior body parts; sunroofs seals 12; electronic circuit boards underthe hood for engine control 16; plastic fascia 20 and may receive paint;and wear surfaces.

An automotive glazing windshield system may include a frame 4 attachedto a vehicular body supersystem 2, a sealant, a primer, and a glasssurface. The glass surface of the windshield 8 may include a frit 10and/or a tinted region 6. Other examples of systems may include anelastomeric trim strip, an adhesive applied to this trim strip; acomponent part or an electronic circuit board under the hood with awaterproof coating with the board connected to the vehicle's electricalsystem.

Referring to FIG. 2, in an atmospheric pressure air plasma (APAP)system, a polymerizable material in the form of prepolymer in afeedstock vessel 22 is supplied in tube 30 metered using a mass flowcontroller 32 and vaporized and mixed with a carrier gas in mixingchamber 38. The carrier gas is supplied from a carrier gas feedstockvessel 36 and introduced through a meter 34 into mixing chamber 38. Thismixture is introduced into an atmospheric pressure air plasma apparatus44 containing the plasma of ionized gas. The ionization gas comes fromthe ionization gas feedstock vessel 40 through a meter 42. The ambientair pressure around the air plasma apparatus ranges from greater than 50kilopascals, 75 kilopascals, or 100 kilopascals and less than 300kilopascals, 250 kilopascals, 200 kilopascals, or 150 kilopascals. Atthe exit nozzle 50, the high-velocity polymer reaction coating mayachieve velocities greater than 10-m/s, 50-m/s, or 75-m/s, and less than200-m/s, 150-m/s, or 125-m/s. The gases exiting the nozzle 50 at atemperature less than 450° C., 400° C., 350° C., 325° C., or 300° C. andgreater than 70° C., 100° C., 125° C., or 150° C.; while the temperatureof the substrate may be less than 95° C., 85° C., 75° C., 70° C., 65°C., 60° C., 55° C., or 50° C., depending upon the conditions ofoperation. This temperature at the substrate allows this process to workwith substrates that are susceptible to heat damage.

The gases from the exit nozzle 50 form a spray pattern with the outerpenumbra 56 having mostly ionized gas for cleaning and/or activating.Closer to the center of the spray pattern is in area of the higherconcentration 54 of high-velocity impact polymer reaction coatingmaterial. The surface 58 receiving the high-velocity impact polymerreaction coating 62 is an automotive glazing glass windshield 28 havinga ceramic frit 60 and tinted glass 64. The windshield is encapsulatedwithin a frame 66.

The surface to receive the layer may be activatable by ionization andheat and may be in pristine condition, have a covering of debris, or becorroded. The surface may be cleaned, and partially activated, by anatmospheric pressure air plasma. Possible cleaning and activationmechanisms of an atmospheric pressure air plasma by itself may includerepair of alkali depleted layers of weathered glass, ionization of thesurface, modification of the surface energy, combustion of oils and dustor combinations thereof. When the atmospheric pressure air plasma isalso a device depositing high-velocity impact polymer coatings of oneembodiment of this invention, the penumbra of the atmospheric pressureair plasma exiting from the nozzle may have a cleaning functionassociated with the ionization and heat. Accordingly, in thisembodiment, the time period between of the cleaning and/or activationstep and the deposition step is greater than 1 μs, 5 μs, 10 μs, 25 μs,or 100 μs.

Another embodiment of this invention includes having one or moreseparate atmospheric pressure air plasmas to clean and/or activate thesurface, followed by one or more separate atmospheric pressure airplasmas depositing high velocity in impact polymer coatings. The APAPsmay be operated in a sequential manner, in a parallel manner or acombination thereof. When operated as a parallel set of multi-APAPstypical spacing may be about 2 mm.

The cleaning and/or activating operation may be capable of operating athigher travel speeds than the deposition operation or a combinedcleaning and/or activating as well as a deposition operation. Otheraspects of these embodiments may include having the cleaning operationusing broader width passes and the deposition operation using theirraster-type passes. The cleaning and/or activating operation may beaccomplished using other ionization technologies such as coronadischarge or combustion sources. Accordingly to this embodiment, thetime periods between the cleaning/activation step and deposition isgreater then 0.1 second, 1 s, 5 s, 10 s, 25 s, or 100 s and less than150 s, 300 s, 10 minutes, 30 min, 1 hour, 12 hr, 1 day, 2 days, or 5days.

An additional embodiment includes the ability to develop gradients ofprepolymers where additional feedstock vessel 24 holding otherprepolymers are fed through supply line 26 to the prepolymer feedstockvessel 22 in order to incrementally adjust the ratio or ratios of theprepolymers in the feedstock. An additional aspect of this embodimenthas the other prepolymers fed through a supply line 28 to a meteringdevice 32 that may be adjusted incrementally or step-wise based on theratio or ratios of prepolymers.

In certain embodiments, the APAP can deliver a plasma air treatment tothe surface coating to reactivate the surface coating. For example, thesurface may be cleaned and coated in one location, and then shipped to asecond location for reactivation at a later time.

Referring to FIG. 3, in an embodiment of the present invention a surface68 has a layered composite formed by a high-velocity impact polymerreaction coating 70 with a CASE compound 72 applied in a separate step,to connect the dissimilar materials of the surface 68 to the portions ofthe frame 74. The CASE compound is cured by light radiation 76 from theAPAP 78 as it passes nearby during a subsequent raster deposition of thehigh-velocity impact polymer reaction coating.

Referring to FIG. 4, in another embodiment of the present invention, alayered composite is formed to protect an electronic circuit board 80and its solder lugs 86 from water, other fluids and vapors. Thehigh-velocity impact polymer reaction coating 82 is applied to allowbonding to the board 80 and the lugs 86 of a further high-velocityimpact polymer reaction coating 84 having waterproofing performanceproperties.

Referring to FIG. 5, in another embodiment of the present invention, araster composite deposition is shown. In this embodiment, the surface 88is treated with an APAP high-velocity impact polymer reaction coating 90derived from one prepolymer. A second deposition 92 is parallel andtranslated from the first. The second deposition 92 may use anindependently selected prepolymer to generate an APAP high-velocityimpact polymer reaction coating.

Referring to FIG. 6, in another embodiment of the present invention,layered composite depositions are shown. In this embodiment, surface 94receives an APAP high-velocity impact polymer reaction coating. In onepass, an unbalanced composite is formed. A first pass 102 is ahigh-volume impact polymer reaction coating derived from a feedstock of100% of a first prepolymer. A second pass 104 has a high-velocity impactpolymer reaction coating derived from a feedstock of a mixture of thefirst prepolymer and a second prepolymer. In the third pass 106, thehigh-velocity impact polymer reaction coating is derived from afeedstock having 100% of the second prepolymer. The surface propertieshave now been modified to accommodate either a subsequent layer, notshown, to provide protective coatings and/or surface properties such asin chemical or biological protection textile surfaces or to provide moredurable wear coatings to the underlying APAP high-velocity impactpolymer reaction coatings.

Referring to FIGS. 7 and 8, a prepolymer delivery system is shown wherethe ionization gas is supplied by a tube 112 into an APAP 114 having anexit nozzle 116 fitted with an atomizing collar 118, which facilitatesthe introduction of prepolymer mist 128 into high-velocity impactpolymer reaction coating material 122. Prepolymer material is fed intoinjector 132, which delivers the material to atomizing jets 133 ofatomizing collar 118 for generating the prepolymer mist 128. Thehigh-velocity impact polymer reaction coating material 122 is applied toa surface 126 as a high-velocity impact polymer reaction coating 124.

Examples of surfaces that may be candidates for activation anddeposition may include, but are not limited to, glassy material, alaminated windshield, glass for a vehicle, glass, corroded glass, glasshaving a frit, tinted glass, silicates, aluminates, borates, zirconia,transition metal compounds, steel, carbonates, bio-compatible material,calcium phosphate mineral, tetracalcium phosphate, dicalcium phosphate,tricalcium phosphate, monocalcium phosphate, monocalcium phosphatemonohydrate, hydroxyapatite, laminated circuit boards, epoxy, wood,textile, natural fiber, thermoplastics, thermoset plastics, a surfacewith a melting temperature greater than 70° C., surfaces havingcomponents that may be susceptible to heat damage, or combinationsthereof. In fritted and tinted glasses, the frit or the tint may be onthe surface, dispersed in the surface, or combinations thereof. Asurface having components that may be susceptible to heat may havecomponents with properties such as melting or re-crystallizingtemperatures of less than 400° C., 350° C., 300° C., 250° C., 200° C.,150° C., 100° C., or less than 100° C. Other indicators of a surfacesusceptible to heat damage may be having a service temperature of lessthan 350° C., 300° C., 250° C., 200° C., 150° C., 100° C., or less than50° C.; or a material that experiences a glass transition temperature ofless than 200° C., 150° C., 100° C., or less than 50° C.

Surfaces may also be considered susceptible to heat damage if they orthe deposit have a coefficient of linear thermal expansion greater thanabout 10×10⁻⁶/° C., 15×10⁻⁶/° C., 20×10⁻⁶/° C., or 50×10⁻⁶/° C.Differential expansion rates between surface and an APAP deposit mayresult in incorrect dimensions or failures due to shear stresses.Surfaces may further be considered susceptible to heat damage if theyhave a chemical decomposition temperature of less than 400° C., 350° C.,300° C., 250° C., or less than 250° C. Decomposition may be consideredan example of reactions where the material or bonds within the surfacematerial chemically cleave. Other examples of chemical reactions wherecleavage may occur are reactions such as combustion, dehydration,decarboxylation, pyrolysis, or oxidation.

Surfaces which are susceptible to heat damage may include those formaking prototype molds and dies, as well as articles requiring repair orprotective coatings. In addition, differences in thermal expansionbetween surface and applied melted material may cause residual stressesin the articles or in the solidified APAP-applied materials. warpedarticles, and fractures from thermal shock. Examples of these surfacecomponents that may be susceptible to heat damage include epoxy tools,silicone molds, tooling boards, modeling boards, foam boards, mediumdensity fiberboards, fiber laminates, pattern lumber, machinable wax,thin shell tooling, and various materials used for rapid prototyping,such as laser-light-cured resins, laminated paper, wax, wood, foamedpolymers, and sintered ceramics.

A surface susceptible to heat damage may also be a thin shell havinglittle bulk into which to transfer excess heat. A typical thin shell maybe less than 25-mm, 20-mm, 15-mm, 10-mm, 5-mm, 4-mm, 3-mm, 2-mm or evenless than 1-mm thick.

A surface susceptible to heat damage may also be a material containingsignificant residual stresses. When exposed to heat of more than 50° C.,100° C., 150° C., or 200° C. and less than 400° C., 350° C., 300° C., or250° C. these residual stresses may be released fully or partially. Theresult may be a dimensional distortion or warping of the surfaces thatmay be susceptible to heat damage.

Plasma polymerization yields polymers in arrangements not typicallyfound under normal chemical conditions. The polymers may be have highlybranched chains, randomly terminated chains, or functional crosslinkingsites. Absent are regularly repeating units, in general. This is aresult of the fragmentation of the prepolymer molecules when they areexposed to the high-energy electrons inherent in the plasma. Thereactions appear to proceed by several reaction pathways including freeradical formation, homolytic cleavage, cationic oligomerization, andcombinations thereof.

The deposit resulting from reaction in an atmospheric pressure airplasma differs from conventional polymers, oligomers, and monomers. Inconventional monomers, oligomers, and polymers there is a standardseries of one or more building block units, also called mers. As thepolymeric chains grow the building block units are repeated andoccasionally cross-linked. In a plasma polymer, the building block unitsmay be fragmented and have new functional groups developed. When theyrecombine, there may be generally higher crosslink density, an increasedpresence of branched chains, randomly terminated chains, or acombination thereof. The crosslink density calculation becomes moredifficult as the number of cross links divided by the number of backboneatoms approaches unity. Such may be the case in plasma polymers. Arelative measure of the crosslink density may be the shift in glasstransition temperature relative to the conventional polymer. One mayexpect that at low degrees of crosslinking the shift upwards of theglass transition temperature will be to the number of crosslinks. Inplasma polymers, the slope of the proportion may increase relatively byabout 10%, 15%, or 20% compared to conventional polymers.

Prepolymers that may be suitable for deposition by atmospheric pressureair plasma include compounds that can be vaporized. The vapors may bemetered and blended with a carrier gas. This mixture of gases may beintroduced into a plasma generated by an atmospheric pressure airplasma. The ionization gas of the atmospheric pressure air plasma may bechosen from gases typical of welding processes which may include, butare not limited to, noble gases, oxygen, nitrogen, hydrogen, carbondioxide, and combinations thereof.

Prepolymers used to create a high velocity impact polymer coating mayinclude, but are not limited to, reactive substituted compounds of group14 such as those corresponding to the formulaR_(a)X_((3-a))M₁-O-M₂R_(b)X_((3-b)), where R is a hydrolysable organicradical possessing functionality imparting a desired characteristic, Xmay be a halogen, M is a group 14 element such as silicon, and O isoxygen; those corresponding to the formula R_(n) M X_((4-n)), where Rmay be a readily-hydrolyzable organic radical, M is a group 14 elementsuch as silicon, and X may be a halogen; those corresponding to theformula R₂ MO, wherein R is a hydrolyzable organic radical, M is a group14 element, and O is oxygen; linear siloxanes; cyclical siloxanes;methylacrylsilane compounds; styryl functional silane compounds; alkoxylsilane compounds; acyloxy silane compounds; amino substituted silanecompounds; hexamethyldisiloxane; tetraethoxysilane;octamethyltrisiloxane; hexamethylcyclotrisiloxane;octamethylcyclotetrasiloxane; tetramethylsilane; vinylmethylsilane;vinyl triethoxysilane; vinyltris(methoxyethoxy) silane;aminopropyltriethoxysilane; methacryloxypropyltrimethoxysilane;glycidoxypropyltrimethoxysilane; hexamethyldisilazane with silicon,hydrogen, carbon, oxygen, or nitrogen atoms bonded between the molecularplanes; organosilane halide compounds; organogermane halide compounds;organotin halide compounds; di[bis(trimethylsilyl)methyl]germanium;di[bis(trimethylsilyl)amino]germanium; organometallic compounds based onaluminum or titanium; or combinations thereof. Candidate prepolymers donot need to be liquids, and may include compounds that are solid buteasily vaporized. They may also include gases that compressed in gascylinders, or are liquefied cryogenically and in vaporized in acontrolled manner by increasing their temperature.

In certain embodiments, the thickness of the high velocity impactpolymer coating may be increased sufficiently to create a seal withportions of a frame. The buildup of thickness can be accomplished byincreasing the time the deposition is allowed to occur; by increasingthe throughput of deposition; by volumizing the deposition; orcombinations thereof. Increasing the time of deposition may involve, butis not limited to, holding the position of the APAP substantially in thesame place for an extended period of time or using multiple APAPs totraverse the same location.

In another embodiment of this invention, multiple APAPs may depositdifferent prepolymers so as to create a layered composite deposition,different prepolymers in different spatial areas to create a rasteredcomposite deposition, or combinations thereof.

Another embodiment of this invention involves applying the prepolymer asa primer using APAP. A second layer may then be applied to the primer toconnect the primer to portions of the frame. In the non-limiting examplewhere the second layer joins a windshield to a frame the bead of thehigh-velocity impact polymer coating may be as wide as 10 mm. The secondlayer typically is as wide or wider than the high-impact polymercoating. A second layer may include, but is not limited to, CASEcompounds, polyurethane compounds, polyimide compounds, metal film,polyamide compounds, varnish, vulcanization compounds, organicmembranes, corrosion-resistant compound, biocompatible coating,hydrophobic coating, hydrophilic compound, siloxane compounds, tincompounds, germanium compounds, ceramic frit, paint, epoxy, orcombinations thereof. CASE compounds include, but are not limited to,protective coatings, anti-wear coatings, corrosion control coatings,paints, conformal coatings, epoxy protective coatings, acrylicprotective coatings, alkyd protective coatings, polyurethane protectivecoatings, pressure sensitive adhesives, emulsion polymers, silicones,wood preservatives, thermoplastic elastomers, medical adhesives,coatings for fabrics, caulks, rubber compounds, powder coatings, carbonblack, radiation-cured (radcure) compounds, and combinations thereof.

The adhesion of the second layer may be analyzed using the Quick KnifeAnalysis method. According to this method, after treatment of a surfaceadhesive beads of a CASE compound are applied to the surface and allowedto dry for a three day period. After three days, they are sliceddiagonally with a razor. The sections are then twisted and pulled untilthey fail either adhesively, cohesively, or a combination thereof. Theresulting failure mode is reported.

The frame may serve to protect and/or connect one or more parts of thedissimilar materials to the supersystem structure. The framing may bemade of any number of materials so long as they suit the design purpose.Examples may include, but are not limited to, a metal channel or apolyurethane cap surrounding automotive glazing glass or solder tabsattached to circuit boards having waterproof coatings.

Example 1

An APAP cleaning and activating step and a deposition of high-velocityimpact polymer reaction coating occur in a single step. While notwanting to be tied to a single theory of operation, it appears that APAPgases exiting from the nozzle have a penumbra of ionized plasma thatperforms a cleaning and activating step, which will be referred tosimply as cleaning, in a first time period followed very quickly and inone step by the deposition of the high-velocity impact polymer reactioncoating which is concentrated at the core of the ionized plasma exitingfrom the nozzle.

In this example, a robotic arm, fitted with a FLUME APAP supplied byPlasma Treat North America, Inc. delivers a high-velocity impact polymerreaction coating derived from a prepolymer of hexamethyldisiloxane(HMDSO). Approximately 30 grams per hour of HMDSO is diluted with 5 Lper minute of air. The mixture of HMDSO and air is introduced to anAPAP. The ionization gas is introduced at 30 L per minute. Thehigh-velocity impact polymer reaction coating is applied to a glass at adistance of 8 mm from the exit nozzle with a robotic arm travel velocityof up to 600 mm per second when directional changes are required such asin a raster pattern with a spacing of 2 mm between passes.

Example 2

In this example, the cleaning and activation step occurs separately fromthe step of depositing the high-velocity impact polymer reactioncoating. An APAP on a robotic arm traces a robotic gas at 25 mm persecond. The same conditions are used as in Example 1.

In this example, a robotic arm, fitted with a FLUME APAP supplied byPlasma Treat North America, Inc. cleans the surface by passing a plasmaover the surface. The ionization gas, air, is introduced at 30 L perminute. The cleaning plasma is applied to a glass at a distance of 8 mmfrom the exit nozzle with a track pitch of 2 mm with a robotic armtravel velocity of up to 600 mm per second when directional changes arerequired such as in a raster pattern with a spacing of 2 mm betweenpasses. A second APAP follows the same robotic travel path as thecleaning plasma and delivers a high-velocity impact polymer reactioncoating derived from a prepolymer of tetraethoxydisiloxane (TES).Approximately 30 grams per hour of TES is diluted with 5 L per minute ofair. The mixture of TES and air is introduced to an APAP. The ionizationgas is introduced at 30 L per minute. The high-velocity impact polymerreaction coating was applied to a glass at a distance of 8 mm from theexit nozzle with a robotic arm travel velocity of up to 600 mm persecond when directional changes are required such as in a raster patternwith a spacing of 2 mm between passes.

Example 3

This example shows that cleaning the surface followed by depositing thehigh-velocity impact polymer reaction coating in either one or two stepsusing an APAP improves adhesion of a second layer to glass relative tosimply cleaning and activating the glass with an APAP, cleaning theglass with a solvent wipe of isopropyl alcohol, or applying theprepolymer by itself to the glass.

The test method to show the adhesion results is the Quick Knife Adhesionmethod. After treatment, adhesive beads of a CASE compound, in this casea polyurethane sealant, are applied to the surface and allowed to dryfor a three day period. After three days, they are sliced diagonallywith a razor. The sections are then twisted and pulled until the beadeither fails adhesively or cohesively. The desired result is cohesivefailure.

The surfaces used included standard automotive glazing windshield glasscorroded automotive glazing in the form of dirty windshield glass thathad been left open to the air for one year; windshield glass having afritted area.

The results of this test are reported in Table 1.

TABLE 1 Corroded Fritted Glass Glass Windshield No Adhesive AdhesiveAdhesive failure treatment failure failure HMDSO Adhesive 70% 95%Adhesive failure; alone failure Adhesive 5% Cohesive failure failure;30% Cohesive failure APAP Cohesive Adhesive Cohesive failure alonefailure failure Isopropyl Adhesive Adhesive Adhesive failure Alcoholfailure failure Solvent wipe APAP + Adhesive Cohesive Cohesive failureHMDSO one failure failure step APAP + Cohesive Cohesive Cohesive failureHMDSO two failure failure stepIn addition, the combination of corroded glass with a frit exposed tothe same corroding conditions exhibited cohesive failure only in atwo-step operation under the same deposition conditions.

Example 4

This example shows creation of layered composite high-velocity impactpolymer reaction coatings. The application conditions are similar toconditions in Example 2.

In this example, a separate APAP cleans and activates the surface. Asecond APAP on a robotic arm applies a 0.1 μm layer of high-velocityimpact polymer reaction coating using HMDSO as the prepolymer. A thirdAPAP on a robotic arm traces the same robotic pass as the second APAPand applies a 0.05 μm layer of high-velocity impact polymer reactioncoating using octamethyltrisiloxane as the prepolymer.

Example 5

This example shows creation of a rastered composite high-velocity impactpolymer reaction coating. The application conditions are similar toconditions in Example 2.

In this example, a separate APAP cleans and activates the surface. Asecond APAP on a robotic arm applies a 0.1 μm layer of high-velocityimpact polymer reaction coating using HMDSO as the prepolymer. A thirdAPAP on a robotic arm traces a robotic pass parallel path which istranslated 2 mm from second APAP path and applies a 0.1 μm layer ofhigh-velocity impact polymer reaction coating usingoctamethyltrisiloxane as the prepolymer.

Example 6

This example shows creation of an embodiment of a graded high-velocityimpact polymer reaction coating. The application conditions are similarto conditions in Example 2.

In this example a separate APAP cleans and activates the surface. Ansecond APAP on a robotic arm applies a 0.1 μm layer of high-velocityimpact polymer reaction coating. The prepolymer starts as a pure HMDSOprepolymer. During a second robotic pass on the same robotic arm travelpath as the first pass, the second APAP uses the prepolymer which isadjusted to an equal volume mixture of HMDSO and octamethyltrisiloxane.During a third robotic pass on the same robotic arm travel path as thefirst pass, the second APAP uses the prepolymer which is adjusted topure octamethyltrisiloxane.

Example 7

In this example, an embodiment is shown where advantage is taken of theability to interrupt application of the high-velocity impact polymerreaction coating and/or the cleaning and activation step to create amask on a surface. The application conditions are similar to conditionsin Example 2.

In this example, a single APAP on a robotic arm cleans and activates thesurface followed within 0.01 second by the deposition of a 1 μm layerthe high-velocity impact polymer reaction coating. Using a preprogrammedsignal, the APAP shuts off the ionization creating the plasma as well asthe flow of the prepolymer. The robotic arm continues travel for adistance. Using a second preprogrammed signal the APAP resumes thecleaning and activation step and the deposition of the high-velocityimpact polymer reaction coating.

After 0.5 seconds, another robotic arm applies a radiation-cured CASEsealant along the same robotic arm travel path that the APAP used. Theinfrared and/or ultraviolet light from the APAP cures the CASE sealant.

In a subsequent operation, the CASE sealant is sliced with a sharpimplement at the interface between the spaces where the high velocityimpact polymer reaction coating and the uncoated areas. The CASE sealantin the uncoated areas is then removed cleanly from the surface becauseit fails adhesively.

Example 8

This example shows that the operating conditions of the plasma affectthe composition of the high-velocity impact polymer reaction coating. Ina physical vapor deposition system with a plasma chamber that isevacuated to 0.027 Pa pressure and the plasma is generated by a 40 kgHertz magnetron, HMDSO prepolymer is injected. A chemical analysis ofthe resultant polymer reaction coating shows a silicon content of 19.8atom percent (at %).

Using the conditions in Example 2, when HMDSO prepolymer is injected,the analysis of the resultant high-velocity impact polymer reactioncoating has a silicon content of 32.0 at %. Coatings using thistechnique may be expected to have silicon content greater than 25 at %.

Example 9

This example describes the temperature of the surface achieved usingdifferent parameters for speed of coating. At a distance between theexit nozzle and surface of 8 mm, when the robotic arm travels at 600mm/second, the surface temperature reaches a maximum of 95° C. When therobotic arm travels at 50 mm/second, the surface temperature reaches amaximum of 180° C.

While the best mode for carrying out the invention has been described indetail, those familiar with the art to which this invention relates willrecognize various alternative designs and embodiments for practicing theinvention as defined by the following claims.

1. A coated substrate surface comprising: a substrate surface; and ahigh-velocity impact polymer reaction coating for promoting adhesivebonding, the coating having first and second opposing surfaces, thefirst opposing surface being adjacent to the substrate surface.
 2. Thecoated substrate surface of claim 1, wherein the high-velocity impactpolymer reaction coating is formed by depositing a polymer reactioncompound onto the substrate surface with a high-velocity impact deviceat a velocity in the range of 10 to 200 meters per second, the polymerreaction compound being formed from substantially random fragmentationof prepolymer molecules.
 3. The coated substrate surface of claim 2,wherein the prepolymer molecules are introduced as a vapor into anatmospheric pressure air plasma to form the polymer reaction compound asa result of the substantially random fragmentation of the prepolymermolecules.
 4. The coated substrate surface of claim 2, wherein theprepolymer molecules have a silicon atom content of at least 25 percent.5. The coated substrate surface of claim 2, wherein the prepolymer is areactive substituted compound of group 14 having the formulaR_(a)X_((3-a))M₁-O-M₂R_(b)X_((3-b)), where R is a hydrolysable organicradical, X is a halogen, M is a group 14 element such as silicon, and Ois oxygen, or the formula R_(n) M X_((4-n)), where R is areadily-hydrolysable organic radical, M is a group 14 element such assilicon, and X is a halogen.
 6. The coated substrate surface of claim 1,wherein the substrate surface is a glass surface.
 7. The coatedsubstrate surface of claim 6 further comprising a frame adjacent to atleast a portion of the second opposing surface of the high-velocityimpact polymer reaction coating.
 8. The coated substrate surface ofclaim 7, further comprising a compound layer having third and fourthopposing surfaces, wherein the third opposing surface is adjacent to thesecond opposing surface of the high-velocity impact polymer reactioncoating and the fourth opposing surface is adjacent to at least aportion of the frame.
 9. The coated substrate of claim 8, wherein thecompound layer is a material chosen from the group consisting ofcoatings, adhesives, sealants, elastomer compounds and combinationsthereof.
 10. The coated substrate surface of claim 6, wherein the glasssurface is an automotive windshield glass surface.
 11. The coatedsubstrate of claim 1, wherein the high-velocity impact polymer reactioncoating is a composite coating formed from two or more different typesof prepolymer molecules.
 12. The coated substrate of claim 1, whereinthe composite coating includes a coating layer derived from a firstprepolymer molecule, a second prepolymer molecule different from thefirst prepolymer molecule, or a mixture thereof.
 13. The coatedsubstrate of claim 12, wherein the first prepolymer molecule ishexamethyldisiloxane.
 14. The coated substrate of claim 12, wherein thesecond prepolymer molecule is tetrathoxydisiloxane.
 15. The coatedsubstrate of claim 12, wherein the second prepolymer molecule isoctamethyltrisiloxane.
 16. A coated glass surface comprising: a glasssurface; and a high-velocity impact polymer reaction coating forpromoting adhesive bonding, the coating having first and second opposingsurfaces, the first opposing surface being adjacent to the substratesurface; wherein the high-velocity impact polymer reaction coating isformed by depositing a polymer reaction compound onto the glass surfacewith a high-velocity impact device at a velocity in the range of 10 to200 meters per second, the polymer reaction compound being formed fromsubstantially random fragmentation of prepolymer molecules introduced asa vapor into an atomospheric pressure air plasma.
 17. The coated glasssurface of claim 16, wherein the prepolymer molecules have a siliconcontent of at least 25 percent.
 18. The coated glass surface of claim 16further comprising a frame adjacent to at least a portion of the secondopposing surface of the high-velocity impact polymer reaction coatingand a compound layer having third and fourth opposing surfaces, whereinthe third opposing surface is adjacent to the second opposing surface ofthe high-velocity impact polymer reaction coating and the fourthopposing surface is adjacent to at least a portion of the frame.
 19. Thecoated glass surface of claim 18, wherein the compound layer is amaterial chosen from the group consisting of coatings, adhesives,sealants, elastomer compounds and combinations thereof.
 20. A coatedsubstrate surface comprising: a substrate surface; and a high-velocityimpact polymer reaction coating for promoting adhesive bonding, thecoating having first and second opposing surfaces, the first opposingsurface being adjacent to the substrate surface; wherein thehigh-velocity impact polymer reaction composite coating is formed bydepositing a polymer reaction compound onto the substrate surface with ahigh-velocity impact device at a velocity in the range of 10 to 200meters per second, the polymer reaction compound being derived fromsubstantially random fragmentation of prepolymer molecules introduced asa vapor into an atomospheric pressure air plasma and wherein thecomposite coating includes a coating layer derived from a firstprepolymer, a second prepolymer different from the first prepolymer, ora mixture thereof.